Red-shifted tris-aryl-s-triazines and compositions stabilized therewith

ABSTRACT

Tris-aryl-s-triazines which contain from one to three resorcinol derived moieties with at least one of said moieties substituted at the 5-position with an alkyl, phenylalkyl, halogen, thio or sulfonyl group have UV spectra which are red-shifted to the near UV range and provide excellent stabilization to polymeric substrates against the deleterious effects of actinic light. ##STR1##

The instant invention pertains to novel red-shiftedtris-aryl-s-triazines and their use in protecting polymer systems proneto degradation caused by actinic radiation.

BACKGROUND OF THE INVENTION

Tris-aryl-s-triazines in which at least one of the aryl groups has anhydroxy group ortho to the point of attachment to the triazine ring arewell known UV absorbers. It is also well-known that this class oftriazines protect organic polymers from the deleterious effects ofexposure to actinic radiation.

For the purposes of this application 2,4-dihydroxyphenyl groups on as-triazine ring may be referred to as resorcinol groups. The numberingsystem used on the resorcinol group is outlined as follows: ##STR2##

U.S. Pat. Nos. 3,118,887 and 3,268,474 describe the protection ofplastic and resinous compositions from UV light by the incorporation ofone or more compounds of the class of tris-aryl-s-triazines. The formerpatent claims 2,4,6-tris-(2,4-dihydroxyphenyl)-s-triazine and2,4,6-tris-(2-hydroxy-4-alkoxyphenyl)-s-triazines. Atris-5-alkylresorcinol-s-triazine is prepared, but not tested orclaimed.

U.S. Pat. No. 3,268,474 claims the composition of a polymeric materialand a tris-aryl-s-triazine that has at least one ortho-hydroxyphenylgroup and which may be further substituted on each of the three arylrings by alkyl, alkoxy, halo, etc., with a total of up to threesubstituents on each ring. Preferred substitution patterns are notgiven. There are specific claims for compositions includingtris-(2-hydroxy-4-alkoxyphenyl)-s-triazines and2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine.Again, an example of a tris-alkylresorcinol-s-triazine is given, but itis not tested and its composition with a polymer is not claimed.

U.S. Pat. No. 3,242,175 claims bis-resorcinol-tris-aryl-s-triazines withno substitution on the resorcinol rings. U.S. Pat. No. 3,244,708 claimsmono-, bis-, or tris-resorcinol-tris-aryl-s-triazines with nosubstitution on the resorcinol rings. A Markush structure in theintroduction of the patent does refer tomono-resorcinol-tris-aryl-s-triazines that may be further substituted onthe resorcinol ring by one or two or combinations of hydroxy, halogen,alkyl, alkoxy, phenyl, or phenylalkyl. Preferred substitution patternsare not mentioned and no such compounds are synthesized or tested.

U.S. Pat. Nos. 4,619,956 and 4,740,542 disclose the use of synergisticamounts of tris-aryl-s-triazines and hindered amine light stabilizers inpolymer film coatings or molded articles against the action of light,moisture and oxygen. The tris-aryl-s-triazines referred to in thesepatents are those described in U.S. Pat. No. 3,268,474. The preferreds-triazine is4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine or4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine.A Markush structure in the patents describes tris-aryl-s-triazines withat least one hydroxy group ortho to the point of attachment to thetriazine ring and which may have up to three substituents on each of thethree aryl rings. These substituents include alkyl, alkoxy, halo, etc.Preferred substitution patterns are not given and no compounds withsubstitution on a resorcinol ring are prepared or tested.

E.P. Application No. 444,323 claims highly-solubletris-aryl-s-triazines, the process for their preparation, and theircomposition with an organic solvent. A specific triazine mentioned asuseful in this process is2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine. Thetris-aryl-s-triazines claimed in this application are based on thosedescribed in U.S. Pat. No. 3,268,474. The preferred triazines aremono-resorcinol-tris-aryl based s-triazines. The preferred Markush groupshows that the resorcinol ring may be further substituted in the5-position with alkyl groups. However, the effects of substitution inthis position are not mentioned, and no such compounds are prepared ortested.

E.P. Application No. 483,488 claims the synergistic stabilizercomposition comprised of a tris-aryl-s-triazine and a hindered amine andthe method of stabilizing a polymer by incorporating such a composition.Again, the triazines claimed in the compositions are based on thosedescribed in U.S. Pat. No. 3,268,474. The preferred triazines arebis-xylyl-resorcinol based s-triazines. The body of the application doesshow a Markush structure of a mono-resorcinol-tris-aryl based s-triazinethat may be further substituted in the 5-position of the resorcinol ringwith alkyl groups. However, no triazines with such further substitutionon the resorcinol ring are prepared or tested.

U.S. Pat. Nos. 4,826,978 and 4,962,142 disclose a class oftris-aryl-s-triazines useful as ultraviolet screens for polymers,including coatings. The triazines are based onbis-resorcinol-phenyl-s-triazines with electron withdrawing groupssubstituted on the phenyl group. No further substitution on theresorcinol groups are referred to.

U.S. Pat. No. 5,106,891 claims coating compositions which contain, asthe UV absorber, a mixture of at least one 2-hydroxyphenylbenzotriazoleand at least one 2-hydroxyphenyltriazine. The triazines described arebased on mono-resorcinol-tris-aryl-s-triazines, with the preferredstructure based on bis-xylyl-resorcinol-s-triazine. The Markushstructure discloses that the aryl groups may be substituted by up tothree hydroxyl, halogenomethyl, alkyl, alkoxy or halogen, orcombinations thereof. Structures are disclosed, therefore, oftris-aryl-s-triazines with substituted resorcinol groups, but preferredsubstitution patterns are not disclosed, and no such compounds areprepared or tested.

E.P. Application No. 434,608 claims an organic material which has beenstabilized against damage by light, heat and oxygen and which contains acombination of a hindered amine and an o-hydroxyphenyl-s-triazine orsaid triazine alone, the process for stabilizing an organic material byincorporation of the combination of a hindered amine and said triazineor triazine alone, novel o-hydroxyphenyl-s-triazines, and the use ofnovel s-triazines as a stabilizer for organic materials. Organicmaterials specifically mentioned are coating binders andradiation-curable coating materials. The preferred triazines aremono-resorcinol-tris-aryl based s-triazines with no further substitutionon the resorcinol ting. A Markush structure is claimed that coverstris-aryl-s-triazines with one or two alkyl- or halo-substitutedresorcinol groups. Preferred substitution patterns are not given, and nocompounds with substituted resorcinol rings are prepared or tested.

E.P. Application No. 442,847 claims a coating composition that containsa binder, a hardening agent, and a tris-aryl-s-triazine as a stabilizeragainst damage by light, heat, and oxygen. Specifically mentioned is theuse of this composition for automobile coatings. Preferred triazines foruse in this composition are mono-resorcinol-tris-aryl based s-triazineswith no substitution on the resorcinol ring. A Markush structure isdescribed in the claim section that includes tris-aryl-s-triazines withone or two resorcinol groups that may be further substituted by alkyl orhalogen. Preferred substitution patterns are not given, and no compoundswith substituted resorcinol rings are prepared or tested.

Copending application Ser. No. 08/189,627 claims a polymer filmcomposition which comprises an electro coat primer, a color coat inadhesion to the electro coat, a clear coat in adhesion to the colorcoat, and a tris-aryl-s-triazine UV absorber in either the color coat orclear coat or both. It is pointed out that a particular subgenus oftris-aryl-s-triazines, those based on his- andtris-resorcinol-tris-aryl-s-triazines are especially effective instabilizing such a coating system. A Markush structure in thecomposition claims describes bis- and tris-resorcinol-tris-aryl-s-triazines that may be substituted on theresorcinol rings by an alkyl of 1 to 6 carbon atoms. Specificsubstitution patterns are not discussed. An example of the preparationof 2,4,6-tris-(2,4-dihydroxy-5-hexylphenyl)-s-triazine is given, butthis compound is not tested.

U.S. Pat. No. 5,298,067 claims a coating material stabilized withmonomers or dimers of mono-resorcinol-tris-aryl based s-triazines aloneor in combination with a hindered amine or anhydroxyphenylbenzotriazole, and the method of stabilizing a coatingmaterial by incorporating these s-triazines. No further substitution onthe resorcinol groups is referred to. A coating material specificallymentioned is an automotive laquer.

E.P. Application No. 165,608 discloses s-triazines including a class oftris-aryl-s-triazines, the process for their preparation, and theirmethod of use as UV absorbers in organic materials, especially colorphotographic materials. Tris-aryl-s-triazines disclosed include thosewith one to three resorcinol groups that may be substituted with alkyl,alkoxy, hydroxy, or alkyl or phenylcarbonyl. Preferred substitutionpatterns are not disclosed. Examples are given forbis-resorcinol-tris-aryl-s-triazines with the resorcinol substituted inthe 3-position by methyl, in the 6-position by hydroxy, methoxy, andmethyl, and in the 5-position by acetyl.

U.S. Pat. No. 3,843,371 claims photographic material which contains atris-aryl-s-triazine as a stabilizer against UV radiation. A Markushstructure in the claims of this patent includesbis-resorcinol-tris-aryl-s-triazines that may have an alkyl substituentin the 6-position of one of the resorcinol rings. Preferred triazinesare bis-resorcinol-tris-aryl based s-triazines with no furthersubstitution on the resorcinol rings. A Markush structure in the body ofthe patent describes tris-aryl-s-triazines that may have one or tworesorcinol groups that may be substituted with halogen, hydroxyl, alkyl,alkoxy, phenyl, phenoxy, cycloalkoxy, etc. Preferred substitutionpatterns are not discussed and no compounds with substituted resorcinolgroups are prepared or tested.

E.P. Application No. 468,921 claims aqueous dispersions of s-triazineswith at least one anionic or non-ionic compound. The Markush structurein the claim section includes tris-aryl-s-triazines possibly having oneresorcinol ring substituted by alkyl or halogen. The substitutionpattern is not specified. The preferred triazines includemono-resorcinol-tris-aryl based s-triazines with no substitution on theresorcinol ring and are the only s-triazines exemplified. U.S. Pat. No.4,831,068 claims a process for stabilizing dyeings on polyester fibermaterials with a s-triazine UV absorber and the polyester fiber materialtreated by such a process. The Markush structure and preferred triazinesare the same as in E.P. Application No. 468,921. Again, only s-triazinesof the preferred type are shown in the examples.

U.S. Pat. No. 4,950,304 claims the process of quenching or suppressingthe fluorescence of natural or synthetic polyamide substrates treatedwith whitening agents. The process comprises applying to said substratesa liquor containing an hydroxyphenylbenzotriazole or anhydroxyphenyltriazine and fixing said UV absorber thereon. The Markushstructure of s-triazines disclosed includes tris-aryl-s-triazines thatmay have a substituted resorcinol group. The resorcinol group may besubstituted in the 3- or 5-position by halogen, alkyl, cycloalkyl,phenylalkyl, sulfo, etc. Preferred triazine structures arebis-phenyl-resorcinol-s-triazines with a sulfonate group substituted inthe 5-position of the resorcinol ring. No s-triazines with resorcinolgroups substituted with any of the other substituents are prepared ortested. The advantage of substitution in the 5-position over the3-position of resorcinol is not discussed.

U.S. Pat. No. 5,096,489 claims a method of stabilizing an ink jet printwith the use of an aqueous solution of a dye in combination with as-triazine. A Markush structure describes tris-aryl-s-triazines that mayhave one or more resorcinol groups substituted in the 5-position by asulfo, halo, or alkyl group. The preferred triazines for use in thismethod are based on bis- and tris-resorcinol-tris-aryl-s-triazines withno substitution on the resorcinol rings. No s-triazines with substitutedresorcinol groups are exemplified. Advantages of substitution in the5-position of the resorcinol ring are not discussed.

Tris-aryl-s-triazines containing a 2,4-dihydroxyphenyl (resorcinol)group are well-known ultraviolet screening agents for the protection oforganic materials. A drawback to commonly usedhydroxyphenyl-tris-aryl-s-triazines is that they cover less of thenear-UV spectrum than other commercially available UV absorbers, i.e.hydroxyphenylbenzotriazoles. A welcome addition to the an therefore,would be to provide tris-aryl-s-triazines that cover more of the near-UVspectrum. This invention discloses novel tris-aryl-resorcinol baseds-triazines that have significant absorbance in the range of 360-400 nm.

DETAIL DESCRIPTION OF THE INVENTION

The instant invention pertains to novel tris-aryl-s-triazines whichcontain at least one, and preferably one, 2,4-dihydroxyphenyl(resorcinol aryl) group substituted in the 5-position with a carbon,halogen, thio, sulfinyl or sulfonyl moiety.

More particularly, the instant invention relates to the compounds offormula I, II, III, IV or V ##STR3## where in the compounds of formula I

X and Y are the same or different and are phenyl or phenyl substitutedwith one to three lower alkyl, halogen, hydroxy or alkoxy;

R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12carbon atoms, halogen, --SR₃, --SOR₃, or --SO₂ R₃ ; or said alkyl orcycloalkyl substituted by one to eight halogen, --R₄, --OR₅, --N(R₅)₂,═NR₅, ═O, --CON(R₅)₂, --COR₅, --COOR₅, --OCOR₅, --CN, --NO₂, --SR₅,--SOR₅, --SO₂ R₅, --P(O)(OR₅)₂, morpholinyl, piperidinyl,2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperazinylgroups or combinations thereof; or said alkyl or cycloalkyl interruptedby one to six phenylene, --O--, --NR₅ --, --CONR₅ --, --COO--, --OCO--,--C(R₅)═C(R₅)-- or --CO-- groups or combinations thereof; or said alkylor cycloalkyl both substituted and interrupted by combinations of thegroups mentioned above;

R₃ is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms. phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 10 carbon atoms or said aryl substituted by one or twoalkyl of 1 to 4 carbon atoms;

R₄ is aryl of 6 to 10 carbon atoms, or said aryl substituted by one tothree halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbonatoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; orphenylalkyl of 7 to 15 carbon atoms, or said phenylalkyl substituted onthe phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms,alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight orbranched chain alkenyl of 2 to 18 carbon atoms;

R₅ is defined as R₄, or R₅ is also hydrogen or straight or branchedchain alkyl of 1 to 24 carbon atoms; or R₅ is a group of the formula##STR4## where T is hydrogen, oxyl, hydroxyl, alkyl of 1 to 12 carbonatoms, said alkyl substituted by at least one hydroxyl or lower alkoxy,benzyl or alkanoyl of 2 to 18 carbon atoms;

R₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atomsor cycloalkyl of 5 to 12 carbon atoms; or said alkyl or cycloalkylsubstituted by one to eight halogen, epoxy, glycidyloxy, furyloxy, --R₄,--OR₅, --N(R₅)₂, --CON(R₅)₂, --COR₅, --COOR₅, --OCOR₅,--OCOC(R₅)═C(R₅)₂, --C(R₅)═CCOOR₅, --CN, --NCO, or ##STR5## orcombinations thereof; or said alkyl or cycloalkyl interrupted by one tosix epoxy, --O--, --NR₅ --, --CONR₅ --, --COO--, --OCO--, --CO--,--C(R₅)═C(R₅)COO--, --OCOC(R₅)═C(R₅)--, --(R₅)C═C(R₅)--, phenylene,or-phenylene-G-phenylene in which G is --O--, --S--, --SO₂ --, --CH₂ --,or --C(CH₃)₂ --, or combinations thereof; or said alkyl or cycloalkylboth substituted and interrupted by combinations of the groups mentionedabove; or R₂ is --SO₂ R₃, or --COR₆ ;

R₆ is straight or branched chain alkyl of 1 to 18 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, phenyl, alkoxy of 1to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms,arylamino of 6 to 12 carbon atoms or a group --R₇ COOH or --NH--R₈--NCO;

R₇ is alkylene of 2 to 14 carbon atoms or o-phenylene;

R₈ is alkylene of 2 to 10 carbon atoms, phenylene, tolylene,diphenylenemethane or a group ##STR6## with the proviso that when R₂ ishydrogen and R₁ is n-hexyl, X and Y are not each5-n-hexyl-2,4-dihydroxyphenyl;

for the compounds of formula II:

X is phenyl or phenyl substituted with one to three lower alkyl,halogen, hydroxy or alkoxy;

R₁ and R₁ ' are the same or different and are defined as R₁ above;

R₂ and R₂ ' are the same or different and are defined as R₂ above; and

with the proviso that when R₁ and R₁ ' are each n-hexyl, and R₂ and R₂ 'are each hydrogen, X is not 5-n-hexyl-2,4-dihydroxyphenyl;

for the compounds of formula III:

R₁, R₁ ' and R₁ " are the same or different and are as defined for R₁above;

R₂, R₂ ' and R₂ " are the same or different and are as defined for R₂above; and

with the proviso than when R₂, R₂ ' and R₂ " are each hydrogen, R₁, R₁ 'and R₁ " are not each n-hexyl;

for the compound of formula IV:

X, X', Y and Y' are the same or different and are phenyl, phenylsubstituted by one to three lower alkyl, halogen, hydroxy or alkoxy;

L is straight or branched chain alkylene of 1 to 12 carbon atoms,cycloalkylene of 5 to 12 carbon atoms, alkylene substituted by orinterrupted by cyclohexylene or phenylene, or L is --S--, --S--S--,--S--E--S--, --SO--, --SO₂ --, --SO--E--SO--, --SO₂ --E--SO₂ --, --CH₂--NH--E--NH--CH₂ -- or ##STR7## where E is alkylene of 2 to 12 carbonatoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted orterminated by cyclohexylene of 8 to 12 carbon atoms;

R₂ and R₂ ' are the same or different and are defined as R₂ is above;and

for the compounds of formula V:

X, Y, and R₁ are defined as above;

n=2 to 4;

when n=2, Q is straight or branched chain alkylene of 2 to 16 carbonatoms; or said alkylene substituted by one to eight --OH; or saidalkylene interrupted by one to eight --CH═CH-- or --O--; or saidalkylene both substituted and interrupted by combinations of the groupsmentioned above; or Q is xylylene or a group --CONH--R₈ --NHCO--, --CH₂CH(OH)CH₂ O--R₉ --OCH₂ CH(OH)CH₂ --, --CO--R₁₀ --CO--, or--(CH₂)m--COO--R₁₁ --OOC--(CH₂)m--,

where m=1 to 3; or Q is ##STR8##

R₈ is defined as above;

R₉ is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by1 to 10 --O--, phenylene, or a group -phenylene-G-phenylene- in which Gis --O--, --S--, --SO₂ --, --CH₂ --, or --C(CH₂)₂ --;

R₁₀ is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by1 to 4 --O--, --S--, or --CH═CH--; or R₁₀ is arylene of 6 to 12 carbonatoms;

R₁₁ is alkylene of 4 to 20 carbon atoms, or said alkylene interrupted by1 to 8 --O--;

when n=3, Q is a group --[(CH₂)_(m) COO]₃ --R₁₂ where m=1 to 3 and R₁₂is an alkanetriyl of 3 to 12 carbon atoms;

when n=4, Q is a group --[(CH₂)_(m) COO]₄ --R₁₃ where m=1 to 3 and R₁₃is an alkanetetryl of 4 to 12 carbon atoms.

Preferably, the invention pertains to compounds of formula I where X andY are phenyl or phenyl substituted with one to three lower alkyl orhalogen;

R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, or phenylalkyl of 7 to 15 carbonatoms;

R₂ is straight or branched chain alkyl of 2 to 24 carbon atoms, or saidalkyl substituted by one or two --OR₅, where R₅ is hydrogen, straight orbranched chain alkyl of 1 to 24 carbon atoms, or phenyl; especiallywhere said alkyl is substituted by one hydroxyl and by one --OR₅ whereR₅ is alkyl of 1 to 24 carbon atoms or phenyl;

or compounds of formula IV where X, X', Y and Y' are phenyl or phenylsubstituted with one to three lower alkyl or halogen;

R₂ and R₂ ' are the same or different and are defined as R₂ is above;

and L is: ##STR9##

Most preferably, the invention pertains to compounds of formula I whereX and Y are phenyl, 2,4-dimethylphenyl, 4-methyl phenyl, or4-chlorophenyl;

R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, or phenylalkyl of 7 to 15 carbonatoms;

R₂ is straight or branched chain alkyl of 2 to 6 carbon atoms, or saidalkyl substituted by one or two --OR₅ where R₅ is hydrogen or straightor branched chain alkyl of 1 to 24 carbon atoms; especially where saidalkyl is substituted by one hydroxyl and by one alkoxy of 1 to 24 carbonatoms.

Some examples of preferred compounds of the instant invention are listedbelow.

a.4,6-bis-(2,4-dimethylphenyl)-2-[4-(3-dodecyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-s-triazine;

b.2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)phenyl]-4,6-bis-phenyl-s-triazine;

c.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine;

d.2-[2-hydroxy-4-octyloxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazine;and

e.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-hexyloxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine.

When any of the groups designated in the formulas is alkyl, such alkylgroups are, for example, methyl, ethyl, isopropyl, n-butyl, tert-butyl,tert-amyl, 2-ethylhexyl, n-octyl, n-undecyl, lauryl, n-heptadecyl andn-octadecyl; when alkylene, such alkylene groups are, for example,ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene and2,2-dimethylpropane-1,3-diyl; when cycloalkylene, such cycloalkylenegroups are, for example, cyclopentylene or cyclohexylene; when phenylsubstituted by alkyl or alkoxy, such groups are, for example, tolyl,xylyl or methoxyphenyl; when cycloalkyl, such groups are, for example,cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl; when phenylalkyl,such groups are, for example, benzyl, α-phenethyl, 2-phenethyl or4-tert-butylbenzyl; or when alkyl which are interrupted by --O-- or--NR₅ -- and can be substituted by OH are, for example, methoxyethyl,ethoxyethyl, butoxyethyl, butoxypropyl, CH₃ OCH₂ CH₂ OCH₂ CH₂ --, CH₃CH₂ OCH₂ CH₂ OCH₂ CH₂ --, C₄ H₉ OCH₂ CH₂ OCH₂ CH₂ --, dodecyloxypropyl,2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, --CH₂CH₂ --NH--C₄ H₉, --CH₂ CH₂ CH₂ NH--C₈ H₁₇, --CH₂ CH₂ CH₂ --N(CH₃)--CH₂CH(C₂ H₅)C₄ H₉, 2-hydroxy-3-nonyloxypropoxy and2-hydroxy-3-dodecyloxypropoxy.

Another feature of this invention are the processes by which theseproducts may be obtained. The construction of the tris-aryl-s-triazinenucleus is well known and is described in U.S. Pat. Nos. 3,268,474 and3,244,708. What is claimed here are the processes by which a resorcinolgroup of a tris-aryl-s-triazine may be "post-alkylated," that is,functionalized by substitution in the 5-position with a saturatedcarbon.

The intermediates and reagents required to make the instant compoundsare largely items of commerce or can be obtained by methods known in theart.

Numerous processes may be employed for this "alkylation". Friedel-Craftsalkylations with alkenes, alkyl halides or alcohols using theappropriate catalyst, e.g. aluminum chloride, p-toluenesulfonic acid,methanesulfonic acid, etc.; reduction of the product of a Friedel-Craftsacylation; metal-phenoxide additions across activated (Michael) orunactivated alkenes, with appropriate counterions being potassium,sodium, aluminum, titanium, etc.

The processes preferably employed are Friedel-Crafts alkylations withalkenes using catalytic amounts of p-toluenesulfonic acid ormethanesulfonic acid; or aluminum phenoxide additions across unactivatedalkenes using catalytic amounts of diisobutylaluminum hydride oraluminum isopropoxide.

The process most preferably employed is the aluminum phenoxide additionof the resorcinol-tris-aryl-s-triazine across an unactivated alkeneusing catalytic aluminum isopropoxide, the reaction being run neat attemperatures between 110° and 250° C. The process is outlined below:##STR10##

The process for making the instant compounds is preferably run with atwo to ten excess equivalent amount of alkene, cycloalkene orphenylalkene compared to the amount of the compound of formula A##STR11##

Still another aspect of the instant invention is a compositionstabilized against the deleterious effects of actinic radiation whichcomprises

(a) an organic material subject to degradation when exposed to actinicradiation, and

(b) an effective stabilizing amount of a compound of formula I, II, III,IV or V.

The organic material is preferably a polymer, especially a high solidsthermoset acrylic/melamine resin or an acrylic urethane resin; mostpreferably a high solids thermoset acrylic/melamine resin.

Preferably, the composition is a polymer film compositions whichcomprises

(a) an electro coat primer in adhesion to a metal substrate,

(b) a base or color coat that is in adhesion to the electro coat andwhich comprises a film-forming binder and an organic pigment or aninorganic pigment or mixtures thereof,

(c) a clear coat that is in adhesion to the base coat and whichcomprises a film-forming binder, and

(d) an effective stabilizing amount, of at least onetris-aryl-s-triazine UV absorber contained in either the base coat orthe clear coat or both base coat and clear coat.

The composition above contains as component (d) between 1 and 20% byweight of the film-forming binder.

Component (d) is preferably incorporated into the base coat.

The instant invention also pertains to the defined above whichadditionally contains an effective stabilizing amount of at least one2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; and

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)phenyl]-s-triazine.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, "Lackkunstharze" (1977), pages 99-123). Othercrosslinking agents include glycouril resins, blocked isocyanates orepoxy resins.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention areapplicable for use in non-acid catalyzed thermoset resins such as epoxy,epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionallymodified with silicon, isocyanates or isocyanurates. The epoxy andepoxy-polyester resins are crosslinked with conventional crosslinkerssuch as acids, acid anhydrides, amines and the like. Correspondingly,the epoxide may be utilized as the crosslinking agent for variousacrylic or polyester resin systems that have been modified by thepresence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

To attain maximum light stabilization, the concurrent use of otherconventional light stabilizers can be advantageous. Examples of suchstabilizers are UV absorbers of the benzophenone, benzotriazole,s-triazine, cyanoacrylate or oxanilide type, or metal-containing lightstabilizers, for example, organic nickel compounds, or hindered aminelight stabilizers. In two-coat systems, these additional lightstabilizers can be added to the clear coat or both in the clear coat andin the pigments base coat.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(α-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutactiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occuring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed fromabout 1 to about 20% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from 1 to 5%; preferably 1.5 to 2.5%.

The resulting stabilized compositions of the instant invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

Other compositions of special interest include those which additionallycontain a UV absorber selected from the group consisting of thebenzophenones, benzotriazoles, cyanoacrylic acid derivatives,hydroxyaryl-s-triazines, organic nickel compounds and oxanilides.

Preferred UV absorbers are selected from the group consisting of2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5octylphenyl]-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(ω-hydroxy-octa(ethyleneoxy)carbonyl)ethylphenyl]-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-2H-benzotriazole,4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'ethyloxanilide,2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine,2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,6-bis(2,4-dimethylphenyl)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazineand 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Additional compositions of interest include those which additionallycontain an effective stabilizing amount of a phenolic antioxidant; thosewhich additionally contain a hindered amine derivative; or whichadditionally contain a phosphite or phosphonite stabilizer.

Compositions of special interest also include those wherein the organicmaterial is an enamel of high solids content used for an industrialfinish; is used as a coil coating; is used as a penetrating wood finishor is used as a film-forming wood finish.

When the instant compounds also contain a reactive functional group,said compounds can be chemically bonded by either condensation or freeradical addition reaction to the polymer substrate. This provides for anon-migrating, non-sublimable UV absorber stabilizer. Such reactivefunctional groups include hydroxy, amino, amido, carboxyl andethylenically unsaturated moieties.

The various organic materials useful in the instant invention aredescribed in detail later in this application as well as are the variouscoadditives whose concomitant use with the instant compounds is oftenfound to be highly beneficial.

The resulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl )-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutaneethylene glycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-ten-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________    methanol       diethylene glycol    octadecanol    triethylene glycol    1,6-hexanediol pentaerythritol    neopentyl glycol                   tris-hydroxyethyl isocyanurate    thiodiethylene glycol                   di-hydroxyethyl oxalic acid diamide    ______________________________________

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________    methanol       diethylene glycol    octadecanol    triethylene glycol    1,6-hexanediol pentaerythritol    neopentyl glycol                   tris-hydroxyethyl isocyanurate    thiodiethylene glycol                   di-hydroxyethyl oxalic acid diamide    ______________________________________

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-dio(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3,5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpipefidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypipefidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpipefidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpipefidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-pipefidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(13-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis-(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetra-5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)iminohexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

The following examples are for illustrative purposes only and are not tobe construed to limit the scope of the instant invention in any mannerwhatsoever.

EXAMPLE 12-(2,4-Dihydroxy-5-hexylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a magneticstirrer, condenser, and a nitrogen atmosphere are charged 5.10 g (16.0mmol) of 2-chloro-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 3.10 g (16.0mmol) of hexylresorcinol, and 40 mL of tetrachloroethane. The mixturebecomes homogeneous with gentle warming after which 2.10 g (16.0 mmol)of aluminum chloride are added quickly in small portions. The mixture isheated for five hours with an oil bath maintained at 148° C., and isallowed to sit overnight at room temperature. Following the addition of200 mL of 2N hydrochloric acid, the mixture is refluxed for two hours.After cooling to room temperature, a portion of ethyl acetate is addedand the layers are separated. The aqueous layer is extracted twice morewith ethyl acetate and the combined organic layers are dried overanhydrous magnesium sulfate. Following filtration, the solvent isremoved under reduced pressure to afford 7.35 g of yellow solid. Thecrude product is recrystallized from ethyl acetate/heptane to yield 4.15g of the title compound as a yellow solid; mp 165°-167° C.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 288; 348 nm (ε 38,000; 16,200).

Analysis: Calcd for C₃₁ H₃₅ N₃ O₂ : C, 77.3; H, 7.3; N, 8.7. Found: C,77.2; H, 7.3; N, 8.7.

EXAMPLE 24,6-Bis-(2,4-dimethylphenyl)-2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-phenoxypropoxy)phenyl]-s-triazine

To a 500 mL round-bottomed flask equipped with a magnetic stirrer,condenser, and a nitrogen atmosphere are charged 3.88 g (8.10 mmol) ofthe product of Example 1, 30 mL of 1,2-epoxy-3-phenoxypropane, and 200mg of triphenylethylphosphonium iodide. The mixture is stirred at anexternal temperature of 210° C. for six hours. After cooling to roomtemperature, excess epoxide is removed under reduced pressure and theresidue is dissolved in a portion of 3:1 heptane:ethyl acetate. Thesolution is passed through a plug of silica gel and the solvent isremoved to yield 7.70 g of orange solid. The crude product is purifiedwith medium pressure chromatography with 3:1 heptane:ethyl acetatefollowed by recrystallization from heptane to afford 1.17 g of the titlecompound as a yellow solid; mp 110°-111° C.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 288; 350 nm (ε 40,500; 19,500).

Analysis: Calcd for C₄₀ H₄₅ N₃ O₄ : C, 76.0; H, 7.2; N, 6.7. Found: C,75.7; H, 7.4; N, 6.5.

EXAMPLE 34,6-Bis-(2,4-dimethylphenyl)-2-[4-(3-dodecyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magneticstirrer, condenser, thermometer, and a nitrogen atmosphere are charged15.0 g (31.1 mmol) of the product of Example 1, 12.0 g (46.9 mmol) ofglycidyl dodecyl* ether, and 770 mg of triphenylethylphosphonium iodide.The mixture is stirred at 210° C. for eight hours. After cooling to roomtemperature, excess epoxide is removed under reduced pressure. The crudeproduct is taken up in ethyl acetate, passed through a plug of silicagel and purified with medium pressure chromatography with 3:1heptane:ethyl acetate to afford 16.4 g of the title compound as anorange glassy solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 290; 350 nm (ε 49,500 and 23,900).

EXAMPLE 42-(2,4-Dihydroxy-5-ethylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL round-bottomed flask equipped with a magnetic stirrer,condenser, and a nitrogen atmosphere are charged 5.14 g (15.9 mmol) of2-chloro-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 2.20 g (15.9 mmol) of4-ethylresorcinol, and 40 mL of tetrachloroethane. After gentle warmingto dissolve the mixture, 2.13 g (15.9 mmol) of aluminum chloride areadded quickly in small portions. The mixture is stirred and heated at anexternal temperature of 145° C. for 5.5 hours. After sitting overnightat room temperature, 200 mL of 2N hydrochloric acid are added and themixture is refluxed for three hours. After cooling to room temperature,a portion of ethyl acetate is added and the layers are separated. Theaqueous layer is extracted twice more with ethyl acetate and thecombined organic layers are washed once with brine and are dried overanhydrous magnesium sulfate. Following filtration, the solvent isremoved under reduced pressure to yield 7.10 g of a yellow solid. Thecrude solid is recrystallized from 3:1 heptane:ethyl acetate to afford2.21 g of the title compound as a yellow solid; mp 193°-195° C.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 288; 348 nm (ε 40,400; 18,300).

Analysis: Calcd for C₂₇ H₂₇ N₃ O₂ : C, 76.2; H, 6.4; N, 9.9. Found: C,76.2; H, 6.4; N, 10.1.

EXAMPLE 52-[2,4-Dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL round-bottomed flask equipped with a magnetic stirrer,condenser, and a nitrogen atmosphere are charged 440 mg(1.11 mmol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 2 mL ofdiisobutylene, and 6 mL of methanesulfonic acid. The mixture is stirredat an external temperature of 75° C. for three hours. The mixture isallowed to cool to room temperature, and equal portions of ethyl acetateand water are added. The layers are separated and the organic layer iswashed once with water, twice with saturated sodium bicarbonatesolution, once with brine and is dried over anhydrous magnesium sulfate.Following filtration, the solvent is removed under reduced pressure toyield 1.28 g of yellow solid. The crude solid is purified with mediumpressure chromatography with 3:1 heptane:ethyl acetate to afford 59 mgof the title compound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 290; 346 nm (ε 29,400; 16,600).

EXAMPLE 62-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magneticstirrer, condenser, dropping funnel, thermometer, and a nitrogenatmosphere are charged 15.0 g (37.8 mmol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 390mg of aluminum isopropoxide. The mixture is heated to 175° C. and 4.47 g(37.9 mmol) of α-methylstyrene are added dropwise at a rate of one dropevery two seconds. A total of six equivalents of a-methyl styrene areadded in this fashion over a 4.5 hour period. After cooling to roomtemperature, the mixture is diluted with ethyl acetate, washed twicewith water and once with brine, and is dried over anhydrous magnesiumsulfate. Following filtration, the solvent is removed under reducedpressure to yield a yellow solid. The crude product is purified withmedium pressure chromatography with 12% ethyl acetate/heptane to afford13.2 g of the title compound as a yellow solid; mp 168°-170° C.

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (ethyl acetate) 290; 347 nm (ε 45,700; 23,300).

EXAMPLE 74,6-Bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine

Following the general procedure of Example 3, 4.59 g (8.91 mmol) of theproduct of Example 6, 3.10 g (16.9 mmol) of glycidyl nonyl* ether, and510 mg of triphenylethylphosphonium iodide are reacted at 160° C. forseven hours. The product is worked up as in Example 3 to afford 3.82 gof title compound as a waxy clear brown solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredproduct; UV λ_(max) (ethyl acetate) 291; 348 nm (ε 36,600; 19,000).

EXAMPLE 84,6-Bis-(2,4-dimethylphenyl)-2-[4-hexyloxy-2-hydroxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a magneticstirrer, condenser, thermometer, and a nitrogen atmosphere are charged5.50 g (10.7 mmol) of the product of Example 6 and 50 mL ofN,N-dimethylformamide. After warming to form a homogeneous solution,0.43 g (17.9 mmol) of sodium hydride and 2.26 g (10.7 mmol) of1-iodohexane are added. The mixture is stirred at 40° C. for four hours.After cooling to room temperature, the mixture is poured into a beakerof water. Vacuum filtration affords 4.64 g of the title compound as ayellow solid; mp 111°-115° C.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredproduct; UV λ_(max) (ethyl acetate) 290; 348 nm (ε 41,700; 22,300).

EXAMPLE 92-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazin

To a 500 mL three-necked, round-bottomed flask equipped with a magneticstirrer, dropping funnel, condenser, thermometer, and a nitrogenatmosphere are charged 5.00 g (14.7 mmol) of2-(2,4-dihydroxyphenyl)-4,6-bis-phenyl-s-triazine and 300 mg of aluminumisopropoxide. The mixture is heated to 160° C. and 17.3 g ofα-methylstyrene are added all at once. After stirring at thistemperature for 26 hours the mixture is allowed to cool and a portion ofheptane is added. Vacuum filtration affords 4.45 g of the title compoundas a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredproduct.

EXAMPLE 102-[2-Hydroxy-5-(1-methyl-1-phenylethyl)-4-octyloxyphenyl]-4,6-bis-phenyl-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with acondenser, magnetic stirrer, thermometer, and a nitrogen atmosphere arecharged 4.00 g (8.71 mmol) of the product of Example 9, 50 mL ofN,N-dimethylformamide and 0.40 g (10 mmol) of sodium hydride (60% inmineral oil). The mixture is heated to an external temperature of 50° C.and 1.68 g (8.70 mmol) of 1-bromooctane are added. The mixture isstirred at this temperature for six hours and is allowed to cool to roomtemperature. The mixture is poured into a beaker of water which isextracted four times with chloroform. The combined chloroform layers arewashed four times with water and dried over anhydrous magnesium sulfateand filtered. The solvent is removed under reduced pressure to afford ayellow oil. The crude product is purified with medium pressurechromatography with 10:1 heptane:ethyl acetate followed byrecrystallization from acetone/water to yield 1.12 g of the titlecompound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 271; 351 nm (ε 44,000; 24,000).

EXAMPLE 112-(5-Chloro-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magneticstirrer, thermometer, condenser, and a nitrogen atmosphere are charged20.0 g (61.9 mmol) of 2-chloro-4,6-bis-(2,4-dimethylphenyl)-s-triazineand 50 mL of tetrachloroethane. The mixture is warmed to dissolve thesolids and 8.24 g (62.0 mmol) of aluminum chloride are added in smallportions all at once followed by 9.00 g (62.1 mmol) of4-chlororesorcinol. The mixture is stirred at 120° C. for four hours.After cooling to room temperature 50 mL of water and 10 mL ofconcentrated hydrochloric acid are added and the mixture is refluxed fortwo hours. After cooling, the mixture is extracted thrice with ethylacetate and the combined organic layers are dried over anhydrousmagnesium sulfate and filtered. The solvent is removed under reducedpressure to yield a yellow solid. Recrystallization from ethylacetate/heptane affords 8.65 g of the title compound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 248; 345 nm (ε 48,000; 19,000).

EXAMPLE 122-(2,4-Dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with amechanical stirrer, condenser, and a nitrogen atmosphere are charged5.33 g (13.0 mmol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 20mL of tetrachloroethane. The mixture is warmed to an externaltemperature of 40° C. and 4.33 g (32.5 mmol) of aluminum chloride areadded quickly in small portions. A solution of 1.20 g (13.0 mmol) ofpropionyl chloride in 20 mL tetrachloroethane is added dropwise over 15minutes. The mixture is stirred at an external temperature of 110° C.for four hours. After cooling to room temperature, 50 mL of water and 6mL of concentrated hydrochloric acid are added and the mixture isstirred with warming for two hours. A portion of ethyl acetate is addedwith warming to dissolve all of the solids. The layers are separated andthe aqueous layer is extracted once more with ethyl acetate. Thecombined organic layers are dried over anhydrous magnesium sulfate andfiltered. The product is allowed to crystallize and 2.14 g of the titlecompound is collected by vacuum filtration as a yellow solid.

¹ H nmr (CDCl₃), infrared and mass spectra are consistent with thedesired compound; UV λ_(max) (ethyl acetate) 270; 338 nm (ε 49,500;17,500).

EXAMPLE 132-[2,4-Dihydroxy-5-(1-isobutylimino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

The product of Example 12 (410 mg, 0.900 mmol) is dissolved inisobutylamine with warming. The solution is allowed to stand for onehour. A portion of water is added, the mixture is vacuum filtered andthe precipitate is washed with ethyl acetate. The solid is air dried toyield 300 mg of the title compound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 276; 348 nm (ε 28,700; 16,100).

EXAMPLE 142-[2,4-Dihydroxy-5-(1-isobutylamino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 100 mL round-bottomed flask equipped with a magnetic stirrer arecharged 67 mg (0.13 mmol) of the product of Example 13, 4 mL of aceticacid, and 50 mg of sodium borohydride. The mixture is stirred for onehour. Portions of ethyl acetate and water are added and the layers areseparated. The organic layer is washed twice with water, twice withsaturated sodium bicarbonate solution, once with brine, and is driedover anhydrous magnesium sulfate. Following filtration, the solvent isremoved under reduced pressure to yield 73 mg of the title compound as aclear yellow oil.

¹ H nmr (CDCl₃), infrared and mass spectra are consistent with thedesired compound; UV λ_(max) (ethyl acetate) 288; 348 nm (ε 28,900;17,500).

EXAMPLES 15-18

Following the general procedure of Example 1, 4 or 11, the substituteds-triazine compounds indicated below are prepared.

    ______________________________________    Ex         2-(2,4-dihydroxy-5- )                                 4,6-di-    ______________________________________    15         methyl            xylyl    16         methyl            phenyl    17         ethyl             phenyl    18         chloro            xylyl    ______________________________________

EXAMPLE 19 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser and a nitrogen atmosphere are charged 21.4 g (80 mmol) of2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture ofisomers). To the beige suspension are added 11.3 g (85 mmol) of aluminumchloride in one portion. The mixture is warmed to ca. 80° C. for 45minutes. 18.8 g (96 mmol) of 4-hexylresorcinol are then added in fiveportions over 40 minutes to the now homogeneous solution. The reactionmixture is heated at 90° C. for 24 hours. After cooling to roomtemperature, the contents of the flask are poured into 100 mL of 12%aqueous hydrochloric acid. The precipitate formed is removed byfiltration, washed to pH 7 with water, rinsed with methanol and dried at70° C. under vacuum. The title compound is obtained as a crude orangeproduct (29.2 g) and melts at 209°-213° C. It can be used withoutfurther purification.

EXAMPLES 20-24

Following the general procedure of Example 5, 6 or 9, the substituteds-triazine compounds indicated below are prepared.

    ______________________________________    Ex         2-(2,4-dihydroxy-5- )                                 4,6-di-    ______________________________________    20         tert-butyl        phenyl    21         dodecyl           phenyl    22         dodecyl           xylyl    23         octyl             xylyl    24         octyl             phenyl    ______________________________________

EXAMPLES 25-33

Following the general procedure of Example 2, 3 or 7, the substituteds-triazine compounds indicated below are prepared.

    ______________________________________    Ex     2-(2-hydroxy- )         4,6-di-    ______________________________________    25     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                                   xylyl    26     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                   xylyl    27     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                   phenyl    28     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                                   xylyl    29     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                   phenyl    30     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                                   phenyl    31     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                                   phenyl    32     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                                   phenyl    33     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                                   phenyl    ______________________________________

EXAMPLE 344,6-Diphenyl-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 20.0 g(47 mmol) of the product of Example 19, 6.5 g (47 mmol) of potassiumcarbonate, 50 mg of potassium iodide, and 50 mL of 2-ethoxyethanol. Thesuspension is warmed to 110° C., and 8.5 g (51 mmol) of 1-bromohexaneare added dropwise over 30 minutes. After 22 hours, the reaction mixtureis cooled to room temperature, the precipitate is removed by filtration,washed with water to pH 6, rinsed with methanol and dried at 70° C.under vacuum. The crude yellow product (19 g) is recrystallized twicefrom 100 mL of 2-ethoxyethanol to give the title compound in a yield of15.6 mg as a yellow solid melting at 140°-141° C., purity 98.8% (DSCassay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 273; 355 nm (ε 42,000; 20,000)

Analysis: Calcd for C₃₃ H₃₉ N₃ O₂ : C, 77.8; H, 7.7; N, 8.2. Found: C,77.6; H, 7.9; N, 8.2.

EXAMPLE 354,6-Bis(2,4-dimethylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 200 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 14.5 g(30 mmol) of the product of Example 1, 4.6 g (33 mmol) of potassiumcarbonate, 50 mg of potassium iodide, and 60 mL of 2-ethoxyethanol. Thesuspension is warmed to 110° C., and 5.5 g (33 mmol) of 1-bromohexaneare added dropwise over 20 minutes. After 16 hours, another portion of1-bromohexane (5.5 g, 33 mmol) is added and heating is continued foranother eight hours. The reaction mixture is cooled to room temperature,the precipitate is removed by filtration, washed with water to pH 6,rinsed with methanol and dried at 70° C. under vacuum. The crude yellowproduct (13.9 g) is recrystallized twice from 300 mL of 2-ethoxyethanolto give the title compound in a yield of 10.7 g as a yellow solidmelting at 78°-80° C., purity 99.1% (DSC assay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 293; 353 nm (ε 42,000; 21,000)

Analysis: Calcd for C₃₇ H₄₇ N₃ O₂ : C, 78.5; H, 8.4; N, 7.4. Found: C,78.0; H, 8.3; N, 7.4.

EXAMPLES 36-45

Following the general procedure of Example 8 or 10, the substituteds-triazine compounds indicated below are prepared.

    ______________________________________    Ex        2-(2-hydroxy- )     4,6-di-    ______________________________________    36        5-hexyl-4-dodecyloxy                                  xylyl    37        5-hexyl-4-dodecyloxy                                  phenyl    38        5-hexyl-4-octyloxy  xylyl    39        5-hexyl-4-octadecyloxy                                  phenyl    40        5-hexyl-4-octadecyloxy                                  xylyl    41        5-α-cumyl-4-dodecyloxy                                  phenyl    42        5-α-cumyl-4-dodecyloxy                                  xylyl    43        5-α-cumyl-4-octyloxy                                  xylyl    44        5-α-cumyl-4-octadecyloxy                                  phenyl    45        5-α-cumyl-4-octadecyloxy                                  xylyl    ______________________________________

EXAMPLE 464,6-Bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(1-hydroxypropyl)phenyl]-s-triazine

To a 500 mL 3-necked, round-bottomed flask equipped with a condenser,magnetic stirrer, thermometer, dropping funnel, and a nitrogenatmosphere are charged 25 mL of tetrahydrofuran and 0.89 g (24 mmol) oflithium aluminum hydride. A solution of 2.00 g (4.42 mmol) of theproduct of Example 12 in 250 mL of tetrahydrofuran is added dropwiseover 30 minutes to the stirred suspension. The mixture is stirred atroom temperature for 3.5 hours and the excess lithium aluminum hydrideis quenched with portions of ethyl acetate followed by water. Anhydrousmagnesium sulfate is added, the mixture is filtered, and the solvent isremoved under reduced pressure. The crude product is purified with flashchromatography with 3:1 heptane:ethyl acetate to afford 0.27 g of thetitle compound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 289; 344 nm (ε 45,000; 18,700).

EXAMPLE 472-(5-Benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with amechanical stirrer, condenser, dropping funnel, and a nitrogenatmosphere are charged 5.57 g (14.0 mmol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 25mL of tetrachloroethane. The mixture is warmed to an externaltemperature of 90° C. and 2.88 g (20.5 mmol) of benzoyl chloride in 20mL of tetrachloroethane are added dropwise over 45 minutes. The mixtureis stirred at an external temperature of 145° C. for six hours and isallowed to sit at room temperature overnight. Fifty mL of water and 5 mLof concentrated hydrochloric acid are added and the mixture is stirredwith warming for three hours. A portion of ethyl acetate is added andthe mixture is warmed to dissolve any organic solids. The layers areseparated, the aqueous layer is washed with ethyl acetate and thecombined organic layers are dried over anhydrous magnesium sulfate andfiltered. The product is allowed to crystallize from solution and 3.55 gof the title compound (off-white needles) are collected by vacuumfiltration.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 282; 340 nm (ε 61,400; 15,600).

EXAMPLE 484,6-Bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(α-hydroxybenzyl)phenyl]-s-triazine

To a 300 mL 3-necked, round-bottomed flask equipped with a droppingfunnel, condenser, magnetic stirrer, and a nitrogen atmosphere arecharged 20 mL of tetrahydrofuran and 0.26 g (6.8 mmol) of lithiumaluminum hydride. A solution of 0.50 g (1.0 mmol) of the product ofExample 47 in 30 mL of tetrahydrofuran is added over ten minutes to thestirred suspension. The mixture is refluxed for two hours and is allowedto cool to room temperature. Excess lithium aluminum hydride is quenchedwith portions of ethyl acetate followed by water. Anhydrous magnesiumsulfate is added, the mixture is filtered, and the solvent is removedunder vacuum to afford 0.35 g of the title compound as a yellow solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the title compound;UV λ_(max) (ethyl acetate) 288; 343 nm (ε 32,400; 13,500).

EXAMPLE 492-(2,4-Dihydroxy-5-phenylthiophenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazin

To a 500 mL 3-necked, round-bottomed flask equipped with a magneticstirrer, condenser, thermometer, and a nitrogen atmosphere are charged1.30 g (3.0 mmol) of the product of Example 11, 5 mL ofN-methylpyrrolidinone, and 0.51 g (9.1 mmol) of potassium hydroxide. Themixture is stirred and heated to 140° C. and 0.33 g (3.0 mmol) ofthiophenol is added all at once. After 15 hours the mixture is allowedto cool to room temperature. A portion of 10% aqueous hydrochloric acidis added with stirring. The mixture is filtered and the solids arewashed with water followed by heptane. The crude product isrecrystallized from ethyl acetate to afford 0.56 g of the title compoundas an off-white solid.

¹ H nmr (CDCl₃) and mass spectra are consistent with the desiredcompound; UV λ_(max) (ethyl acetate) 289; 339 nm (ε 51,000; 18,000).

EXAMPLE 502-(2,4-Dihydroxy-5-phenylsulfinylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL 3-necked, round-bottomed flask equipped with a condenser,magnetic stirrer, thermometer, and a nitrogen atmosphere are charged0.25 g (0.49 mmol) of the product of Example 49, 0.059 g (0.98 mmol) ofacetic acid, and 20 mL of 2-propanol. The mixture is heated to refluxand 0.067 g (1.0 mmol) of 50% hydrogen peroxide are added. The mixtureis refluxed for one hour and is allowed to cool to room temperature. Aportion of ethyl acetate is added and the organic layer is washed twicewith 10% aqueous sodium metabisulfite, twice with saturated sodiumbicarbonate, once with brine, and is dried over anhydrous magnesiumsulfate. After filtering, the solvent is removed under reduced pressureto yield a yellow solid. Purification by flash chromatography with 3:1heptane:ethyl acetate yields 0.11 g of the title compound as a yellowsolid.

¹ H nmr (1,1,2,2-tetrachloroethane-d₂) spectrum is consistent with thedesired compound; UV λ_(max) (tetrahydrofuran) 279; 373 nm (ε 23,000;23,000).

EXAMPLE 512-(2,4-Dihydroxy-5-phenylsulfonylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL 3-necked, round-bottomed flask equipped with a magneticstirrer, condenser, thermometer, and a nitrogen atmosphere are charged0.27 g (0.54 mmol) of the compound of Example 50, 0.80 g (1.3 mmol) ofacetic acid, 0.10 g (1.0 mmol) of sulfuric acid, and 20 mL of2-propanol. The mixture is heated to reflux and 0.077 g (1.1 mmol) of50% hydrogen peroxide are added. After five hours, the mixture isallowed to cool to room temperature and a portion of ethyl acetate isadded. The organic layer is washed twice with 10% aqueous sodiummetabisulfite, twice with saturated sodium bicarbonate, once with brine,and is dried over anhydrous magnesium sulfate. After filtering, thesolvent is removed under reduced pressure to afford a yellow solid.Purification with flash chromatography with 1:3 heptane:ethyl acetateaffords 0.11 g of the title compound as a yellow solid.

¹ H nmr (tetrahydrofuran-d₈) and mass spectra are consistent with thedesired compound; UV λ_(max) (ethyl acetate) 276; 377 nm (ε 30,000;31,000).

EXAMPLES 52-53

Using the general procedures of Examples 5, 6 and 9, the followingcompounds of formula IV are prepared.

    ______________________________________    Ex     X, X, Y, Y'                      R.sub.2 and R.sub.2 '                                 L    ______________________________________    52     xylyl      hydrogen   1-(2,2-isopropyli-                                 dene)-4-methyl-1,4-                                 cyclohexylene    53     xylyl      hydrogen   α,α,α',α'-tetramethyl                                 -                                 m-xylylene    ______________________________________

EXAMPLE 54 2-(5-Chloro-2,4-dihydroxyphenyl)-4,6-diphenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser and a nitrogen atmosphere are charged 26.8 g (100 mmol) of2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture ofisomers). To the beige suspension are added 14.9 g (112 mmol) ofaluminum chloride in one portion. The mixture is warmed to ca. 80° C.for 2 hours. 17.4 g (120 mmol) of 4-chlororesorcinol are then added infive portions over 40 minutes to the now homogeneous solution. Thereaction mixture is heated at 90° C. for 42 hours and refluxed foranother 24 hours. After cooling to room temperature, the contents of theflask are poured into 100 mL of 12% aqueous hydrochloric acid. Theprecipitate formed is removed by filtration, washed to pH 7 with water,rinsed with methanol and dried at 70° C. under vacuum. The titlecompound is obtained as a crude ocher-red product (29.5 g) and melts at255°-265° C. It can be used without further purification.

EXAMPLE 554,6-Diphenyl-2-(5-chloro-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 26.3 g(70 mmol) of the product of Example 54, 10.6 g (77 mmol) of potassiumcarbonate, 50 mg of potassium iodide, and 50 mL of 2-ethoxyethanol. Thesuspension is warmed to 110° C., and 10.8 g (77 mmol) of 1-bromohexaneare added dropwise over 30 minutes. After 8 hours, the reaction mixtureis cooled to room temperature, the precipitate is removed by filtration,washed with water to pH 6, rinsed with methanol and dried at 70° C.under vacuum. The crude beige product (26.9 g) is recrystallized twicefrom 600 mL of 2-ethoxyethanol to give the title compound in a yield of18.6 g as a yellow solid melting at 147°-149° C., purity 98.7% (DSCassay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 281; 351 nm (ε 45,000; 18,400)

EXAMPLE 56 4,6-Diphenyl-2-(5-hexyl-4-methoxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 20.0 g(47 mmol) of the product of Example 19, 7.2 g (52 mmol) of potassiumcarbonate and 100 mL of 2-ethoxyethanol. The suspension is warmed to 50°C., and 13.3 g (94 mmol) of methyl iodide are added dropwise over 45minutes. After 14 hours, the reaction mixture is cooled to roomtemperature, the precipitate is removed by filtration, washed with waterto pH 6, rinsed with methanol and dried at 70° C. under vacuum. Thecrude yellow product (16.1 g) is recrystallized thrice from2-ethoxyethanol to give the title compound in a yield of 9.8 g as ayellow solid melting at 186°-188° C., purity 94.1% (DSC assay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 275; 354 nm (ε 41,900; 18,500)

Analysis: Calcd for C₂₈ H₂₉ N₃ O₂ : C, 76.5; H, 6.7; N, 9.6. Found: C,75.3; H, 6.8; N, 9.4.

EXAMPLE 572-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-diphenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, and a nitrogen atmosphere are charged 8.5 g (20 mmol) of theproduct of Example 19, 0.4 g (1 mmol) of triphenylethylphosphoniumbromide, 3.0 g (22 mmol) of butyl glycidyl ether and 50 mL of xylene(mixture of isomers). The thick orange suspension is refluxed for 24hours. The reaction mixture is then cooled to room temperature, theprecipitate is removed by filtration, washed with a small amount ofxylene, rinsed with methanol and dried at 70° C. under vacuum. The crudeyellow product (9.0 g) is recrystallized twice from 20 mL of2-ethoxyethanol to give the title compound in a yield of 6.0 g as ayellow solid melting at 145°-146° C., purity 98.2% (DSC assay).

1H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 275; 354 nm (ε 43,000; 19,000)

Analysis: Calcd for C₃₄ H₄₁ N₃ O₄ : C, 73.5; H, 7.4; N, 7.6. Found: C,73.6; H, 7.5; N, 7.5.

EXAMPLE 582-(2,4-Dihydroxy-5-hexylphenyl)-4,6-bis(4-methylphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser and a nitrogen atmosphere are charged 29.6 g (100 mmol) of2-chloro-4,6-bis(4-methylphenyl)-s-triazone, and 100 mL of xylene(mixture of isomers). To the beige suspension are added 11.3 g (85 mmol)of aluminum chloride in one portion. The mixture is warmed to ca. 90° C.for 75 minutes. 21.4 g (110 mmol) of 4-hexylresorcinol are then added infive portions over 45 minutes to the now homogeneous solution. Thereaction mixture is heated at 90° C. for 18 hours. After cooling to roomtemperature, the contents of the flask are poured into 120 mL of 6%aqueous hydrochloric acid. The precipitate formed is removed byfiltration, washed to pH 7 with water, rinsed with methanol and dried at70° C. under vacuum. The title compound is obtained as a crude orangeproduct (43.1 g) and melts at 228°-231° C. It can be used withoutfurther purification.

EXAMPLE 594,6-Bis(4-methylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 200 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 13.6 g(30 mmol) of the product of Example 58, 4.6 g (33 mmol) of potassiumcarbonate, 50 mg of potassium iodide, and 70 mL of 2-ethoxyethanol. Thesuspension is warmed to 110° C., and 5.5 g (33 mmol) of 1-bromohexaneare added dropwise over 30 minutes. After 20 hours, another portion of1-bromohexane (5.5 g, 33 mmol) is added and heating is continued foranother 25 hours. The reaction mixture is cooled to room temperature,the precipitate is removed by filtration, washed with water to pH 6,rinsed with methanol and dried at 70° C. under vacuum. The crude yellowproduct (13.6 g) is recrystallized from 350 mL of 2-ethoxyethanol togive the title compound in a yield of 10.6 g as a yellow solid meltingat 137°-138° C., purity 96.9% (DSC assay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 293; 354 nm (ε 56,000; 21,500)

Analysis: Calcd for C₃₅ H₄₃ N₃ O₂ : C, 78.2; H, 8.1; N, 7.8. Found: C,77.5; H, 8.2; N, 7.8.

EXAMPLE 602-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2hydroxyphenyl]-4,6-bis(4-methylphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, and a nitrogen atmosphere are charged 13.6 g (30 mmol) of theproduct of Example 58, 0.6 g (1.5 mmol) of triphenylethylphosphoniumbromide, 4.5 g (33 mmol) of butyl glycidyl ether and 40 mL of xylene(mixture of isomers). The thick orange suspension is refluxed for 21hours. The reaction mixture is then cooled to room temperature, theprecipitate is removed by filtration, washed with water, rinsed withmethanol and dried at 70° C. under vacuum. The crude yellow product (14g) is recrystallized twice from 50 mL of 2-ethoxyethanol to give thetitle compound in a yield of 9.3 g as a yellow solid melting at163°-164° C., purity 98.8% (DSC assay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 293; 351 nm (ε 59,000; 20,000)

Analysis: Calcd for C₃₆ H₄₅ N₃ O₄ : C, 74.1; H, 7.8; N, 7.2. Found: C,73.4; H, 7.8; N, 7.1.

EXAMPLE 612-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, and a nitrogen atmosphere are charged 14.4 g (30 mmol) of theproduct of Example 1, 0.6 g (1.5 mmol) of triphenylethylphosphoniumbromide, 4.5 g (33 mmol) of butyl glycidyl ether and 40 mL of xylene(mixture of isomers). The thick orange suspension is refluxed for 24hours. The reaction mixture is then cooled to room temperature, theprecipitate is removed by filtration, washed with water, rinsed withmethanol and dried at 70° C. under vacuum. The filtrate is concentratedon a rotary evaporator to yield a second crop of crude product. Thecombined solids (14.9 g) are recrystallized from 45 mL of2-ethoxyethanol to give the title compound in a yield of 9.0 g as ayellow solid melting at 101°-102° C., purity 97.3% (DSC assay).

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 292; 350 nm (ε 49,000; 21,000)

Analysis: Calcd for C₃₈ H₄₉ N₃ O₄ : C, 74.6; H, 8.1; N, 6.9. Found: C,74.5; H, 8.0; N, 6.9.

EXAMPLE 62 2,4-Bis(2,4-dihydroxy-5-hexylphenyl)-6-phenyl-s-triazine

To a 750 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 34.0 g(150 mmol) of 2,4-dichloro-6-phenyl-s-triazine, 44.0 g (330 mmol) ofaluminum chloride and 100 mL of ligroin (boiling range 110°-140° C.). Tothat suspension, 60 mL of sulfolane are added dropwise with stirringover a 15 minute period with the temperature rising to 50° C. A solutionof 62.1 g (320 mmol) of 4-hexylresorcinol in 60 mL of sulfolane is thenadded dropwise over a 15 minute period. The temperature rises to 60° C.and hydrogen chloride is evolved. The reaction mixture is heated to 80°C. for four hours. The lower layer of the two-phase mixture is pouredinto a solution of 50 mL of concentrated hydrochloric acid in 500 mL ofmethanol and 300 mL of water. The mixture is stirred at room temperaturefor 14 hours. The product obtained is suspended in 800 mL of water at80° C. for 1 hour, is isolated by filtration and resuspended under thesame conditions, finally isolated and dried at 85° C. under vacuum. Thetitle compound is obtained as a crude orange product (77.0 g) and meltsat 230°-238° C. It can be used without further purification.

¹ H nmr (DMSO-d⁶) spectrum is consistent with the desired product.

Analysis: Calcd for C₃₃ H₃₉ N₃ O₄ : C, 73.2; H, 7.3; N, 7.8. Found: C,73.2; H, 7.3; N, 7.6.

EXAMPLE 632-4-Bis[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-6-phenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, and a nitrogen atmosphere are charged 16.2 g (30 mmol) of theproduct of Example 62, 1.1 g (3 mmol) of triphenylethylphosphoniumbromide, 8.6 g (66 mmol) of butyl glycidyl ether and 120 mL ofmesitylene. The thick orange suspension is heated at 130° C. for 18hours to form a brown solution. The solvent is removed using a rotaryevaporator. The crude product is dissolved in 100 mL of ethyl acetate.The solution is filtered through a pad of 230-400 mesh silica (100 g, 10cm diameter) using 1000 mL of ethyl acetate as eluent. After evaporationof the solvent, the yellow resin (25.9 g) is redissolved in 50 mL ofethyl acetate and precipitated with 150 mL of hexane to give 20 g ofproduct. This material is recrystallized from 70 mL of ethyl acetate anddried at 75° C. under vacuum to give the 15.9 g of the title compound asa resinous orange solid melting at 108°-115° C.

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 298; 369 nm (ε 37,000; 38,000)

Analysis: Calcd for C₄₇ H₆₇ N₃ O₈ : C, 70.4; H, 8.4; N, 5.2. Found: C,70.2; H, 8.4; N, 5.1.

EXAMPLE 642,4-Bis(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-6-phenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer,condenser, dropping funnel and a nitrogen atmosphere are charged 16.2 g(30 mmol) of the product of Example 62, 3.7 g (66 mmol) of powderedpotassium hydroxide and 100 mL of 2-ethoxyethanol. To the resulting redsolution are then added 10.9 g (66 mmol) of 1-bromohexane are addeddropwise over 30 minutes. The mixture is heated to 90° C. for 20 hoursand filtered hot. The filtrate is warmed to 100° C. and 1 mL of aceticacid is added. The solution is cooled to 0° C. to give a precipitate.The crude yellow product is recrystallized from 70 mL of 2-ethoxyethanolto give the title compound in a yield of 13.1 g as a yellow solidmelting at 118°-121° C.

¹ H nmr (CDCl₃) spectrum is consistent with the desired product; UVλ_(max) (chloroform) 301; 371 nm (ε 33,000; 40,000)

Analysis: Calcd for C₄₅ H₆₃ N₃ O₄ : C, 76.1; H, 8.9; N, 5.9. Found: C,76.2; H, 8.9; N, 5.9.

EXAMPLE 652-[2,4-Dihydroxy-5-(1-propenyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 100 mL round-bottomed, three-necked flask equipped with a magneticstirrer, condenser, dropping funnel and a nitrogen atmosphere arecharged 410 mg(10.0 mmol) of sodium borohydride and 30 mL of anhydrousethanol. A solution of 500 mg (1.1 mmol) of the product of Example 12 in10 mL of ethanol is added dropwise over a 35 minute period. The mixtureis heated to 68° C. and stirred for three hours. The mixture is allowedto cool to room temperature and is quenched with 10 mL of 2Mhydrochloric acid. A portion of ethyl acetate is added and the layersseparated. The organic layer is dried over anhydrous magnesium sulfate,filtered and the solvent removed under reduced pressure. The crudeproduct is purified with medium pressure chromatography with 3:1heptane:ethyl acetate to afford 34 mg of the title compound as a yellowsolid.

¹ H nmr (CDCl₃), infrared and mass spectra are consistent with thedesired compound; UV λ_(max) (ethyl acetate) 286; 352 nm (ε 44,000;12,500).

EXAMPLE 66 Delamination Resistance of High Solids Thermoset AcrylicClear Coats Containing UV Absorbers Applied over UV Transparent BaseCoats

Test panels are prepared by spray applying a 1.8-2.0 mil (0.036-0.051mm) thick film of a commercially available high solids thermoset acrylicmelamine clear coat, containing 2% by weight, based on the acrylicmelamine resin, of a test UV absorber stabilizer of this invention, overa commercially available UV transparent base coat, wet-on-wet. Thetopcoat is applied over 4"×12" (10.16 cm×30.48 cm) UNIPRIME® panelsobtained from Advance Coatings Technology, Inc. The coated panels arethen baked at 250° F. (121 ° C.) for 30 minutes. After storage for oneweek in an air-conditioned room, the panels are exposed in Florida at 5°South, black box according to SAE J-1976. The panels are exposed for oneyear. After one year, a humidity test is conducted consisting ofexposing the panels to 100° F. (38° C.) and 100% humidity for four days.After four days, a tape adhesion test is performed.

The instant compounds are effective in improving adhesion of the clearcoat to the base coat during weathering.

EXAMPLE 67 Delamination Resistance of Acrylic Urethane Clear CoatsContaining UV Absorbers Applied Directly over Electrocoat Primer

Test panels are prepared by spray applying a 1.8-2.0 mil (0.036-0.051mm) thick film of a commercially available acrylic urethane clear coat,containing 2% by weight, based on the acrylic urethane resin, of a testUV absorber stabilizer of this invention, directly over 4"×12" (10.16cm×30.48 cm) UNIPRIME® panels obtained from Advance Coatings Technology,Inc. The coated panels are then baked at 250° F. (121° C.) for 30minutes. After storage for one week in an air-conditioned room, thepanels are exposed in Florida at 5° South, black box according to SAEJ-1976. The panels are evaluated every day for delamination and areretired from the test when delamination is evident over 10% of the panelarea.

The instant compounds am effective in delaying delamination of the clearcoat from the electrocoat primer.

EXAMPLE 68

The following example demonstrates the utility of theo-hydroxyphenyl-s-triazines of the instant invention in a laminatedpolycarbonate plaque wherein the UV absorber is incorporated only intothe thin surface protecting layer such as prepared in a coextrudedarticle.

Laminated plaques are prepared by bonding a 1 mil (0.0254 mm)polycarbonate film (LEXAN® 141-111N), General Electric Co.) containing5% by weight of an UV absorber to a non-UV stabilized 125 mil (3.18 mm)polycarbonate plaque (LEXAN® 141-111N) via compression molding in aWabash Compression molder at 350° F. (177° C.) for three minutes at 1000psi (70 Kg/cm²), three minutes at 3000 psi (210 Kg/cm²), and then threeminutes at 3000 psi (210 Kg/cm²) while cooling. The plaques are thenexposed in an Atlas CI-65 Xenon Arc Weatherometer, using the ASTMdesignation G26-88 Test Method C with the protective layer facing theincident light. Polymer degradation is determined by measuringyellowness index (YI) on an ACS spectrophotometer.

The o-hydroxyphenyl-s-triazines of the instant invention are veryeffective in protecting the polycarbonate sheet from degradation anddiscoloration.

EXAMPLE 69

Polypropylene fiber samples are prepared by extruding fiber gradepolypropylene containing a pigment, a phosphite, a phenolic antioxidantor hydroxylamine, a metal stearate, a UV absorber or hindered aminelight stabilizer or a combination of a UV absorber and hindered aminelight stabilizer.

The pigment is added as a pigment concentrate which is prepared frompure pigment and polypropylene resin (PROFAX® 6301, Himont) by mixingthe two components in a high shear mixer in a ratio of 25% pigment and75% resin, pressing the resulting resin/pigment mixture on a WabashCompression Molder (Model #30-1515-4T3) into a thin sheet and thendividing the sheet into fine chips for dispersion in fresh polypropyleneresin at reduced concentrations.

All additive and pigment concentrations in the final formulations areexpressed as weight percent based on the resin.

The formulations contain 0.05-0.1% phosphite, 0-1.25% phenolicantioxidant, 0-0.1% hydroxylamine, 0.05-0.1% calcium stearate, 0-1.25%UV absorber of this invention and/or 0-1.25% hindered amine stabilizer.The materials are dry-blended in a tumble dryer, extruded on aSuperior/MPM 1" (2.54 cm) single screw extruder with a generalall-purpose screw (24:1 L/D) at 475° F. (246° C.), cooled in a waterbath and pelletized. The resulting pellets are spun into fiber at about525° F. (274° C.) on a HILLS Research Fiber Extruder (Model # REM-3P-24)fitted with a 41 hole, delta configuration spinnerette. The spun tow isstretched at a draw ratio of 3.2:1 producing a final denier of 615/41.

The fiber samples are knitted into socks on a Lawson-Hemphill FiberAnalysis Knitter, cut into appropriate lengths and exposed in an AtlasCi65 Xenon Arc Weather-Ometer at 89° C. black panel temperature, 0.55W/m² at 340 nanometers and 50% relative humidity (Society of AutomotiveEngineers SAE J 1885 Test Procedure).

Fiber samples are tested by performing color measurements on an AppliedColor Systems spectrophotometer by reflectance mode according to ASTM D2244-79 at regular intervals. Identical, but separate, samples areexamined for catastrophic failure.

While the UV absorbers of this invention do not adequately protect thepigmented polypropylene fiber from actinic induced degradation when usedin the absence of a hindered amine, the combination of a UV absorber ofthis invention with a hindered amine provides far superior protection tothe pigmented polypropylene fiber, indeed synergistic stabilizationprotection over the level of protection provided by the hindered aminealone when used at the same total concentration.

The same superior stabilization is seen when the pigmented polypropylenefiber is replaced with pigmented nylon or polyester fiber.

What is claimed is:
 1. A compound of formula I, II or III ##STR12##where in the compounds of formula I X and Y are the same or differentand are phenyl or phenyl substituted with one to three lower alkyl,halogen, hydroxy or alkoxy;R₁ is phenyl alkyl of 7 to 15 carbon atoms;R₄ is aryl of 6 to 10 carbon atoms, or said aryl substituted by one tothree halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbonatoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; orphenylalkyl of 7 to 15 carbon atoms, or said phenylalkyl substituted onthe phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms,alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight orbranched chain alkenyl of 2 to 18 carbon atoms; R₅ is defined as R₄, orR₅ is also hydrogen or straight or branched chain alkyl of 1 to 24carbon atoms; or R₅ is a group of the formula ##STR13## where T ishydrogen, oxyl, hydroxyl, alkyl of 1 to 12 carbon atoms, said alkylsubstituted by at least one hydroxyl or lower alkoxy, benzyl or alkanoylof 2 to 18 carbon atoms; R₂ is hydrogen, straight or branched chainalkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; orsaid alkyl or cycloalkyl substituted by one to eight halogen, epoxy,glycidyloxy, furyloxy, --R₄, --OR₅, --N(R₅)₂, --CON(R₅)₂, --COR₅,--COOR₅, --OCOR₅, --OCOC(R₅)═C(R₅)₂, --C(R₅)═CCOOR₅, --CN, --NCO, or##STR14## combinations thereof; or said alkyl or cycloalkyl interruptedby one to six epoxy, --O--, --NR₅ --, --CONR₅ --, --COO--, --OCO--,--CO--, --C(R₅)═C(R₅)COO--, --OCOC(R₅)═C(R₅)--, --(R₅)C═C(R₅)--,phenylene, or -phenylene-G-phenylene in which G is --O--, --S--, --SO₂--, --CH₂ --, or --C(CH₃)₂ --, or combinations thereof; or said alkyl orcycloalkyl both substituted and interrupted by combinations of thegroups mentioned above; or R₂ is --SO₂ R₃, or --COR₆ ; R₆ is straight orbranched chain alkyl of 1 to 18 carbon atoms, straight or branched chainalkenyl of 2 to 18 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms,phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbonatoms or a group --R₇ COOH or --NH--R₈ --NCO; R₇ is alkylene of 2 to 14carbon atoms or o-phenylene; R₈ is alkylene of 2 to 10 carbon atoms,phenylene, tolylene, diphenylenemethane or a group ##STR15## for thecompounds of formula II: X is phenyl or phenyl substituted with one tothree lower alkyl, halogen, hydroxy or alkoxy; R₁ and R₁ ' are the sameor different and are defined as R₁ above; R₂ and R₂ ' are the same ordifferent and are defined as R₂ above; andfor the compounds of formulaIII: R₁, R₁ ' and R₁ " are the same or different and are as defined forR₁ above; R₂, R₂ ' and R₂ " are the same or different and are as definedfor R₂ above.
 2. A compound according to claim 1 where in the compoundsof formula I, X and Y are phenyl or phenyl substituted with one to threelower alkyl or halogen;R₂ is straight or branched chain alkyl of 2 to 24carbon atoms, or said alkyl substituted by one or two --OR₅, where R₅ ishydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, orphenyl.
 3. A compound according to claim 2 wherein R₂ is alkyl of 2 to24 carbon atoms substituted by one hydroxyl and by one --OR₅ where R₅ isalkyl of 1 to 24 carbon atoms or phenyl.
 4. A compound according toclaim 1 where in the compounds of formula I, X and Y are phenyl,2,4-dimethylphenyl, 4-methyl phenyl, or 4-chlorophenyl;R₂ is straight orbranched chain alkyl of 2 to 6 carbon atoms, or said alkyl substitutedby one or two --OR₅ where R₅ is hydrogen or straight or branched chainalkyl of 1 to 24 carbon atoms.
 5. A compound according to claim 4wherein R₂ is alkyl of 1 to 24 carbon atoms substituted by one hydroxyland by one alkoxy of 1 to 24 carbon atoms.
 6. The compound according toclaim 1 which isa.2-[2,4-dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine;b.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine;c.4,6-bis-(2,4-dimethylphenyl)-2-[4-hexyloxy-2-hydroxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine;d.2-[2,4-dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazine;e.2-[2-hydroxy-5-(1-methyl-1-phenylethyl)-4-octyloxyphenyl]-4,6-bis-phenyl-s-triazine;or s.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-hexyloxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine.7. The compound according to claim 6 which isa.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine;b.2-[2-hydroxy-4-octyloxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazine;or c.4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-hexyloxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine.